Resin-dyes of the cyanine type



Patented May 19, 1953 UNITED STAT ES PATENT OFFICE RESIN-DYES OF THE CYANINE TYPE Robert- H. Sprasguse; Leslie G. S. Brooke'r, and Samuel Gr. Dent, Jr., Rochester, N. Y., assignorsto Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey NoDrawing. Application September 29,1949, Serial No. 118,702

8 Claims, (01. 260-240) Thisv invention relates cyanine' type.

A large number of cyanine dyes are known,

. and such dyes have been widely used. to sensitardingsuch diffusion, however some" of the methods have been somewhat short of asatisfact'ory solution to the problem.

We have now found a new" method for retarding the diifusion of dyes of thecyanine-type from gelatin layers in which they have been incorporated.

It is, therefore, an object of our invention to provide new resin-dyes of the cyanine type. A further object is to provide a method for preparin such dyes. A still further object is to provide photographic silver-halide emulsions, filter layers comprising such dyes, and a method for preparing such emulsions: and filter layers.

- Other objects will become apparent from a consideration of the following. description and examplesi According to our invention, we prepare new l resin-dyes of the cyanine type, by reactin a dye of. the cyanine type which. contains. a hydroxyalkyl attached to one of the auxochromophoric nitrogen atoms. of said dye with a. vinylenepolymer: containing carboxyli'c halide. and/or anhyd'ride. groups.

Vinylene polymers containing carboxylic halide ('e. g. chloride, bromide, etc.) and/r. anhydride groups include the interpolymers of maleic anhydride, e. g. interpolymers of maleic anhydride with styrene, vinyl acetate, vinyl chloride, alkyl vinyl ethers (-e. g. ethyl vinyl ether, etc), acrylic acid, e-m'ethacryl ic acid, etc., as well as the correspondinginterpolymers oil maleyl and iumaryl halides (e. g. chlorides, bromides, etc.)

to resin-dyes of the with these compounds; pelyacry-lyl halides, e. g.

2 Patent 2,047,398, dated July 14, 1936; Useful polymers of acrylic halides (i. e. acrylic and .methacrylic halides), which can be used in practicing our invention, are described Markand Fikentscher U. S. Patent 1,984,417, dated December 18', 1934. Such polymers include polyacrylyl chloride, poly w-methacrylyl chloride, etc. as well as copolymers' of these halides. with a vinyl compound, such asvinyl acetate, styrene, ethyl acrylate, acrylonitri-le, etc.

As dyes. of the cyanine type, the dyes selected from those represented by the following general formulas can be used:

I and 1%. wherein (Z, n and p each represents a positive integer. from 1 to 2, X, X1. and. X2. each represents an acid radical, e. g. chloride, bromide, iodide, perchlorate, acetate, ethylsulfate, thi'ocyanate, p-toluenesulfonate, ben'zenesulfonate, suliamate, etc.; R and R3 eae'li represents an alkyl group, e. g. methyl, ethyl, n-propyl, n-butyl, allyl, fi-hydroxyethyl, y-hy'droxypropyl, fi-methoxy'ethyl, B-ethoxyethyl, c-acetoxyethyl, benzyl, etc. groups; R1, R2 and R5 each represents a hydroxyalkyl group, e. g. c-hydroxyethyl, 'yhydroxypropyl, fi-hydroxypropl, fi-hydrox-yisopropyl, etc.; R4 represents a hydrogen atom or an alkyl group, e. g. methyl, ethyl, etc.; irrepresents a methenyl group (unsubstituted and substituted, e. g. by a methyl ethyl, n-propyl, benzyl, or phenyl group); T represents a hydroxyl group or a dialkylamino (e. g. dimethylamino diethylamino, ethylmethylamino, etc.) group; Z4 represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the yrrole series;, an'd Z, Z1, Z2 and" Z3 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the oxazoleseries (ct g. methyl,. 4.-phenyloxazole, 4-ethyloxazole, 4,5-diphenyloxazole, S-phenyloxazole), the benzoxazole series (e. g. benzoxazole, 5-chlorobenzoxazole, B-phenylbenzoxazole, 5-methylbenzoxazole, 5-hydroxybenzoxazole, 5-methoxybenzoxazole, etc.), the naphthoxazole series (e. g. anaphthoxazole, B-naphthoxazole, etc.) the thiazole series (e. g. thiazole, e-methylthiazole, 4- phenylthiazole, 4,5-diphenylthiazole, S-phenylthiazole, 4,5 dimethylthiazole, 4-(2-thieny1)- thiazole, etc.), the benzothiazole series (e. g., benzothiazole, 4-phenylbenzothiazole, 5-pheny1- benzothiazole, -methylbenzothiazole, 5-methylbenzothiazole, 5-methoxybenzothiazole, 5-ethoXybenzothiazole, fi-methylbenzothiazole, 6-methoxybenzothiazole, fi-ethoxybenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylencbenzothiazole, tetrahydrobenzothiazole, 5-bromobenzothiazole, 5-iodobenzothiazole, -ethoxybenzothiazole, etc.), the naphthothiazole series (e. g. maphthothiazole, fi-naphthothiazole, etc.), the

'selenazole series (4-inethylselenazole, -phenyl- Dyes selected from those represented by Formula I above can be prepared according to the methods described in Brooker et al. U. S. Patent 2,213,238, dated September 3, 1940, which gives details for anumber of the dyes represented by Formula I. The dyes selected from those represented by Formula II above can be prepared by methods described in Brooker et a1. U. S. Patent 2,231,653, dated February 11, 1941, as well as by methods hereinafter set forth. The dyes selected from those represented by Formula III above can advantageously be prepared by the method hereinafter set forth. In addition to the dyes represented by Formula II above, similar dyes which can be used include those described in Muller 'etal. U. S. Patent 2,280,253, dated April 21, 1942, 'for example, dyes represented by the following "formulas:

The following examples illustrate representative methods for preparing some of the dyes of the cyanine type, which can be converted to resin-dyes according to our invention.

Example A.--3-ethyZ-1'-c-hydroa:yethyZ-2',5-dimethyZora-S'-pyrrolocarbocya.nine iodide 43.4 g. of 2-,B-acetanilidovinylbenzoxazole ethiodide and 28 g. of 1-e-hydroxyethyl-2,5-dimeth ylpyrrole were heated together in 250 cc. of acetic anhydride solution at the refluxing temperature for 45 minutes. After chilling, the solid was collected on a filter, washed with acetone and then water. The yield of dye was 66% crude and 58% after one recrystallization from methyl alcohol. The orange plates had a melting point of 238- 240 C. with decomposition.

Example B.-2-p-hydroa:ystyrylquinoline 5- hydroxyethobromzde A few drops of piperidine was added, with stirring, to the fused mixture of 4.5 g. of quinaldine ,e-hydroxyethoorcmide and 3.0 g. of p-hydroxybenzaldehyde, and the whole was warmed over a free flame for 3 minutes. The solid was dissolved in methyl alcohol. The yield of once recrystallized dye was 78%. The reddish-orange needles had a melting point of 259-26'0 C. with decomposition.

2-p-dimethylaminostyrylquinoline B-hydroxyethobromide represented by the formula:

was obtained by replacing the p-hydroxybenzaldehyde in the above example by a molecularly equivalent amount of p-dimethylaminobenzaldehyde.

In like manner, by replacing the quinaldine p-hydroxyethobromide by a molecularly equivalent amount of 2-methylbenzothiazole c-hydroxyethobromide and the p-hydroxybenzaldehyde by a molecularly equivalent amount of p-dimethylaminobenzaldehyde in the above example, 2-p-dimethylaminostyrylbenzothiazole B- hydroxyethobromide represented by the following formula:

CH3 CCH=CHON/ OH; BI CHaCHa-OH was obtained.

Where a vinylene polymer containing carboxylic anhydride groups is condensed with one of the cyanine dyes selected from those represented by the above general formulas, the condensation can advantageously be carried out in the presence of a few drops of a strong acid, which catalyzes the opening of the carboxylic anhydride rings. Useful acids include sulfuric.

((2.. g. N-methylpiperidine, 126), These tertiary amines also provide aconwar-lient asseco --ohosphoria, benzenesnlfzcnia, etoluencsulfonic, ,ctlianesuifonic. ethanedisulfonic, etc. acid-s, although other acids, canv be, used to advanta Gondensation. of yinylene polymers containing :carboiorlichalideand/or anhy ride group wi h I 'oneof thecyanine dyesselected from. those representedby the abovegeneraiiormulas can: alter- .natively. he catalyzed.- by a tertiary amine. Useizul' tertiary amines include the trialkylamines (e. g. triethyiamzine, tri-n-butylainme, etc),

-N;N.diaikyianilines (e. g. N-,'N-dimethylaniline,

NJN diethylaniline, etc), alkylp-iperidines N-ethyipiperidine pyridine. quinoline, isoquinoline, etc.

reaction medium in which the condensations can be carried out, Inert solvents, e. g. aliphatic and aromatic hydrocarbons (e. .g. n-hexane, n-heptane, benzene, toluene; thexylenes, etc;), halogenated hydrocarbons (e. g. chloroformgethylene dichloride, etc), high boiling ethers (e. g. 1,4- dioxane, n-amyl ether, etc.), ketones .(e. g. acetone, n-butyl methyl ketone, n-bntyl ethyl ketone, eta); phenols. *(e. g; phenol, oand p-crcsols, etcd, etc. can be employed. to advansage.

Heat accelerates the condensations and temamine present, etc.

'- The following examples. serve to illustrate more fully the manner whereby we practice our invention.

I .Emamplel 11 (1 mol.) of 3-ethyl-l dhydroxyeth yi- 29,5'-dimethylnxa-3r--pyrrolocar bocyanine iodide represented by the following formula:

4,5. g; .(1 mol. plus 1.00% excess) or, polyacryly-l chloride. and 26.0v cc. of dry chlorciorm were heated together to the boiling point. There were 'thenadded cc. of dry pyridine, and, them-ixture was, boiled under reflux for 24 hours.

The chloroform was distilled off, 200 cc. of water added and the mixture distilled until 50 cc. of the water had been removed. The mixture was cooled to room temperature, the water decanted .oif from-the rubbery brown nroduct and the latter extracted with cast ho methylalcchcl. The residue Was discarded and the alcohol extract wasconcentrated to dryness, 113 g. of noncrystalline brown solid, representing a 92% yield, were obtained- The product was then dissolved in 200 cc, of methyl alcohol for testing as a filter dye.

Emcmple .2

1.5 g. of,1'-ethyl&3-B5Iwdroxyethyl-5"-methoXYthta-Z'wyanine bromide. (melting at 250 261 C. with decomposition) represented. by the following formula:

0.6 g. of a maleic anhydride-vinyl acetate interpolymer (111 mol. ratio), 20 cc. of chlorotorm and 7 dross of sulfuric acid were heated together at the refluxing temperature for one hour with occasional shaking. After chilling, the dye was collected on a filter. It was dissolved in 25 cc. of cresol, and this solution was added to 300cc. of methyl alcohol, from which the dye was precipitated by the addition of 300 cc. or ether. The dye was collected on a filter as an orange plastic-like mass, weighing 1.1 g. It sensitized a photographic gelatino-silver bromoiodide emulsion to about 570 m with maximum sensitivity at about 540 m A resin-dye exhibiting similar sensitizing action can be obtained by replacing the maieic anhydride-vinyl acetate interpolymer used in the above example by a molecularly equivalent amount of polymethacrylic anhydride.

Emample 3 1.0 g. on? l'-n-butyl-33 -fl-hydroxyethylthiai' carbocyanine iodide imelting at 272-273 C. with decomposition) represented by the following tor-mule.

and 1.0 g. of a maleic anhydride-vinyl acetate interpolymer (1:1 mol. ratio) were dissolved in it cc. of cresolat 100 (3., after adding 8 drops to about 40 ce. with acetone and ether, and centrifuged. The plastic-like mass was given a further washing with acetone, the residue Weighing 1.3 g. after drying. This dye sensitized a photographic gelatino-sil-ver bromoiodide emulsion from about 580 to 690 m with maxima sensitivity at about 665 m andabout 5'85 m By replacing the 1-n-butyl-3-B-hydroxyethylthia-4" -oarbocy-anine iodide of the above enarnple with a molecularly equivalent amount of i ethyl 1"- v -hydroxypropyl-2,2'-cyanine iodide represented by the following formula:

a resin-dye can be obtained which sensitizes about that portion of the spectrum wherein the unreacted dye exhibits its sensitizing action,

Czlr I CHzOHrOH a resin dye exhibiting sensitizing action can be obtained.

Example 4 1.4 g. of 2-p-hydroxystyrylquinoline c-hydroxy- .ethobromide represented by the following formula:

and 1.0 g. of a maleic anhydride-vinyl acetate interpolymer (1:1 mol. ratio) Were dissolved in cc. of cresol at 100 C., and after adding 8 drops of sulfuric acid, the reaction mixture was heated for about 2 minutes at about 100 C. The yellow solution was cooled, acetone added, and the dye precipitated by cautiously adding ether. The mixture was centrifuged, the liquors decanted and the residue then stirred with acetone. After centrifuging, the acetone washings were decanted. The dye was then washed with Water, ether and again with acetone.

By replacing the maleic anhydride-vinyl acetate interpolymer with a like amount of a maleic anhydride-styrene interpolymer (1:1 mol. ratio) in the above example, a resin-dye can also be obtained.

Example 5 1.0 g. of 2-p-dimethylaminostyrylquinoline c-hydroxyethobromide represented by the following formula:

was placed in a beaker, acetone added and the mixture stirred. The acetone washings were decanted, and the dye residue dissolved in methyl alcohol, then precipitated by adding ether. When the mixture was filtered, the dye remained as a sticky residue on the filter paper.

Example 6 1.0 g. of 2-p-dimethylaminostyrylbenzothiazole c-hydroxyethobromide represented by the following formula:

s OH;

and 0.45 g. of a maleic anhydride-vinyl acetate interpolymer were ground together and then heated in 20 cc. of chloroform containing 10 drops of sulfuric acid at the refluxing temperature for about 30 minutes. After chilling, the dye was collected on a filter, stirred in a beaker with acetone and the acetone washings decanted. The residue was dissolved in methyl alcohol, and the dye precipitated by adding ether. After drying, 1.1 g. of product were obtained.

' By replacing the 2-p-dimethylaminostyrylbenzothiazole B-hydroxyethobromide used in the above example with a molecularly equivalent amount of 3-ethyl-3-c-hydroxyethylthiaselenacarbocyanine bromide represented by the following formula:

a plastic-like resin-dye can be obtained.

By replacing the cyanine type dyes containing hydroxyalkyl groups and vinylene polymers-containing ,carboxylic halide and/or anhydride groups used above with other representative substances selected from those set forth above, other resin-dyes exhibitingsensitizing action or lightfiltering properties can be obtained, using the procedure set forth in detail in the above illustrative examples. It can be readily seen that our new resin-dyes can be prepared by a single condensation involving a combination of a dye of the cyanine type containing a hydroxyalkyl group with a vinylene polymer containing carboxylic halide and/or anhydride groups. Variations in combinations can expeditiously be made by varying the reactants according to directions hereinbefore set forth.

While our invention has been described with particular reference to monomethine, carbocyanine and styryl dyes containing a hydroxyalkyl group, other dyes containing a hydroxyalkyl group which can also be employed in practicing our invention include merocyanine, oxonol and hemioxonol dyes. The hydroxyalkyl group can be attached to the heterocyclic nucleus through a linkage other than the NC bond illustrated, e. g. to a carbon atom of the nucleus through an intermediate sulfur or oxygen linkage thus C-SC (hydroxyalkylmercapto) or C-OC (hydroxyalkoxy). Groups other than hydroxyalkyl groups, which react with carboxylic halide or anhydride groups, can be utilized in place of the hydroxyalkyl groups illustrated to give new resin dyes. Such groups include, for example, amino, N-monoalkylamino, hydroxyl, etc. groups. The following examples illustrate this useful alternative.

Example 7 3.46 g. of 3-amino-4-[(3-ethyl-2(3)-benzoxazolylidene) -ethylidene] -1-phenyl-5 pyrazolone represented by the following formula:

and 1.84 g. of a maleic anhydride-vinyl acetate interpolymer (1:1 mol. ratio) were ground together, and then heated in 25 cc. of chloroform ctntain ing 1-0 drops of sulfuric acid at the refluxing temperature for 50 minutes. After Cooling, the solid was collected on a fi1ter=andwashed with methyl alcohol. The filter cakewas then extracted with 125 cc. of .hot methyl alcohol. When this extract was chilled, 1.1 g. Of an orange amorphous solid separated. It sensitized a photographic gelatino silver .chlorobromide emulsion to about 520 Hi l with maximum sensitivity at about 485 m The '3 amino-4- [(3 -eth 'yl-2=(3) benzonaaclfliclenelethylidenel-1-phenyl-5-pyra2oione used the above example was obtained as follows:

1.0 g. (1 11101.) of triethylamine was added to a suspension of 4.34 g. (1 mol.) of 2-,8-acetaniiidovinylbenzoxazole ethiodide and 1. 1 g. -(1 mol.) of 3-amino-1-phenyl-5-pyrazo1one in 50 cc. of absolute ethyl alcohol, and the reaction mixture was heated at the refluxing temperature for minutes. After chilling, the solid was collected on a filter and washed with methyl alcohol. The yield of dye was 84% crude and 64% after two recrystallizations from methyl alcohol. The reddish orange crystals had a melting poi-lit of 286 207 C. with decomposition.

Ezrampled 3:46 g. "of "i--[ (8-ethy1-2-'('-3)benzoxazolylidene) ethylidenel -'3-hydroxyl-phenyl 5 pyrazolone represented by the following formula:

/ o=oN-oiH5 o=onon=o N and 1.84 g. of a maleic anhydride-vinyl acetate interpolymer (1:1 mol. ratio) were ground together and then heated in 325 cc. of chloroform containing 10 drops of sulfuric acid. After cooling the mixture, the dye Was collected on a filter and washed with methyl alcohol. It showed sensitization of a photographic gelatino-silverchlorobromlde emulsion to about 520 m with maximum-sensitivity atabout 480 me.

The '4- [(3 ethyl 2(3) benzoxaz'olylidene) ethylidenel 3 hydroxy-1-phen'yl-5 pyrazolone used in'the above example was'obtained as fob lows:

1.0 g. (1 mol.) of triethylamine was addedto a suspension of 4134 g. (1 mol.) of '2-B-acetan'i1i'dovi'nylb'enzoxazo'le ethiodide and 1.76 g. (1 mol.) of "3-hydroXy-1-phenyl 5 pyrazolon'e 50 ccxo'f absolute ethyl alcohol, and the reactionm'ixture was heated at the refluxing 'temperatureffor "10 minutes. After chilling, the solid was collected on 'afilter andwashe'd with methyl alcohol. The yield of dye was 95% crude and 52% 'aftertwo recrystallizations from 'methyl alcohol. The yellow crystals had 'amelting point of 313-318 Ciwithdecomposition.

Where the resin-dyes of our invention have been obtained irom'a 'vinylene polymer containing carbo'xylic halide groups, the "products are generally heated for a short period in the'presence of water to hydrolyze unreacted Ih'a'l'ide groups to carboxylic groups. This :procedure is 'followed'inExamplel above.

' In the .p'reparation'of photographic sil'verh'al- 'ide emulsions containing those of our new resin- 'dyes which exhibit sensitizing action, it is only necessary to disperse the dyes in'the emulsions. Ordinarily this is advantageously accomplished by dissolving the dyes in methanol or ethamil,

or :a mixture of the two, and dispersing the re-- sulting solution in the emulsion. Seine of the less sombre dyes can be converted to their salt forms and dissolved more readily, either in water, or the alco'hols listed above, this form. Quite unexpectedly, we have found that certain of the less solu lole' dyes of the 'cyanine type, when reacted with certain vinylene polymers containing carboxyli'c halide anclior anhydride according to our invention, can be *dissolved or dispersed more readily than the unreac'ted dye in solvents, e. :g. methanol or ethanol. The salts are advantageously formedhy adding to the resin-"dye, wet with a little water,' methanol or ethanol, 'to an alkali metal hydroxide, e. g. sodium or potassium hydroxide, or ammonium hydroxide, or an amine, e. g. methylamine, ethylamine, dimethylamine, diethylamine, trime'thyl-amine, triethylamine, ethanolamine, diethanolamine, triethanol-amine, pyridine, N methylpiperidine, n propylamine, isopropylamine, butylamine, ,d-ethoxyethyla min-e, etc., and taking-up the salt which forms in a suitable =solvent, e. g. methanol, ethanol, a mixture of methanol and ethanol, etc.

Sensitization by means of our new resin-dyes is primarily directed to the ordinarily employed gelatino-silver-halide developing-out emulsions, e. g. 'gelatino-silver-chloride, chlorobromide, -chlorobromiodide, -.bromide and -bromiodide developing-out emrilsions- The resin-dyes, or the salt iormsof thesedyes, are advantageous'lyadded to the finished emulsions and should, of course, be uniformly distributed throughout the emulsions.

The concentration of these compounds in the emulsion can vary widely, e. g. from about .5 to about 100,mg.per liter of 'flowable emulsion. The concentration of the dye will vary according to the type of light-sensitive material and according to the effects desired. The most suitable and most economical concentration for any given emulsion will be apparent to those skilled in the art, upon'ma' king the ordinary tests and observations customarily used in the art of emulsion making. To prepare a gelatino silver-halide emulsion sensitized with one of our new resindyes, the toll owing procedure is satisfactoryiz a quantity of'the resin-dye, or the salt form of the dye, is dissolve-min methanol, ethanol, -or:a mix ture :of methanol and ethanol, and a volume of the solution containing from 5 to mg. of'idye is slowly added to about 1600 cc. of a gelatinosilver-ha'lide emulsion with stirring. Stirring .is continued until the resin-dye, or the salt form-of the resin-dye, is uniformly dispersed. With .the more powerful of our new sensitizing dyes, .10t0 50 mg. of dye per 1000 .cc. of emulsion .suiiice to produce the maximum sensitizing effect with'the ordinary gelatino-silver halide emulsions.

The above statements are only illustrative and are not to be understood as limiting our invention any sense, as 'it will'be-apparent that our new resin-dyes or the salt forms of these dyes canhe incorporated by other methods in many of the photographic emulsions customarily employed in the art,'such, for instance, as by bathing a plate or iilm upon which an emulsion is coated, in a solution of the dye (or its salt form) in an appropriate-solvent, although such :a method is ordinarily not to be preferred.

In the preparation of photographic silver halide emulsions "containmg our new resin-dyes (or the salt f-orms thereof") which can "advantageously be used for the preparation of o-vercoaiting layers, filter layers, etc., the following procedure'can be used: from 50 mg. to 150 mg. of the resin-dye, or the salt form of the dye, are dissolved in from 2 to cc. of a water-miscible solvent. Methanol, or ethanol is suitable for this purpose, but other solvents can also be used. The solution is then added to about 25 cc. of a 5% gelatin solution at 40 C. and the mixture coated on the support.

What we claim as our invention and desire protected by Letters Patent of the United States is:

1. A resin-dye selected from those represented by the three following general formulas:

Z2 .g ecncmsw mhgi wherein d, n and p each represents a positive integer from 1 to 2, X, X1 and X2 each represents an acid radical, R and R3 each represents a primary alkyl group containing from 1 to 4 carbon atoms, R1, R2 and R5 each represents a hydroxyalkyl group containing from 2 to 3 carbon atoms, the hydroxyl group of said hydroxyalkyl groups having been esterified by a polymer of a monomer selected from the group consisting of an 11,5- ethylenically-unsaturated, aliphatic hydrocarbon carboxylic halide containing from 3 to 4 carbon atoms and an a,5-ethylenically-unsaturated, aliphatic hydrocarbon carboxylic anhydride containing from 4 to 12 carbon atoms, R4 represents a member selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group, L represents a methenyl group, T represents a member selected from the group consisting of a hydroxyl group, a dimethylamino group and a diethylamino group, Z4 represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the pyrrole series, and Z, Z1, Z2 and Z3 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of oxa- -zo1e series, the benzoxazole series, the nathphoxazole series, the thiazole series, the benzothiazole series, the naththothiazole series, the selenazole series, the benzoselenazole series, the thiazoline series, the 3,3-dimethylindolenine series, the quinoline series and the pyridine series.

2. A resin-dye represented by the following .general formula:

CHaO S 3. A resin-dye represented by the following gen eral formula:

wherein R2 represents a fi-hydroxyethyl group, the hydroxyl group of which has been esterified by an interpolymer of maleic anhydride and vinyl acetate.

4. A resin-dye represented by the following formula:

wherein R5 represents a ,B-hydroxyethyl group, the hydroxyl group of which has been esterified by polyacrylyl chloride.

5. A process for preparing a resin-dye comprising reacting a dye selected from those represented by the three following general formulas:

wherein d, n and p each represents a positive integer from 1 to 2, X, X1 and X2 each represents an acid radical, R and R3 each represents a primary alkyl group containing from 1 to 4 carbon atoms, R1, R2 and R5 each represents a hydroxyalkyl group containing from 2 to 3 carbon atoms, R4 represents a member selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group, L represents a methenyl group, T represents a member selected from the group consisting of a hydroxyl group, a dimethylamino group and a diethylamino group, Z4 represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the pyrrole series, and Z, Z1, Z2 and Z3 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those ,of oxazole series, the benzoxazole series, the

naphthoxazole series, the thiazole series, the benzothiazole series, the naphthothiazole series, the selenazole series, the benzoselenazole series, the thiazoline series, the 3,3-dimethylindolenineseries, the quinoline series and the pyridine series, with a polymer of a monomer selected from the group consisting of an a,/3-ethy1enica1lyunsaturated, aliphatic hydrocarbon carboxylic halide containing from 3 to 4 carbon atoms and an 11,,8- ethylenically-unsaturated, aliphatic hydrocarbon carboxylic anhydride containing from 4 to 12 carbon atoms.

13 6. A process for preparing a resin-dye comprising reacting 1'-ethyl-3- 3-hydroxyethyl-6-methoxythia-2-cyanine bromide represented by the following formula:

C=CH-CH=CH \N ClHi-OH with an interpolymer of maleic anhydride and vinyl acetate.

7. A process for preparing a resin-dye comprising reacting 2-p-dimethylaminostyrylbenzothiazole p-hydroxyethobromide represented by the following formula:

C-CH=CHON\ N/ CH: 02114 011 Br with an interpolymer of maleic anhydride and vinyl acetate.

8. A process for preparing a resin dye compris- 14 ing reacting 3-ethyl-1-p-hydroxyethyl-2',5'-dimethyloxa 3' pyrrolocarbocyanineiodide represented by the following formula:

with polyacrylylchloride.

ROBERT H. SPRAGUE. LESLIE G. S. BROOKER. SAMUEL G. DENT, JR.

' References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,178,612 Schneider Nov. 7, 1939 2,186,731 Schneider Jan. 9, 1940 2,186,733 Schneider Jan. 9, 1940 2,307,399 Frohlich Jan. 5, 19. .3

FOREIGN PATENTS Number Country Date 532,098 Great Britain of 1941 

1. A RESIN-DYE SELECTED FROM THOSE REPRESENTED BY THE THREE FOLLOWING GENERAL FORMULAS: 